Liquid-crystalline compounds

ABSTRACT

Liquid-crystalline compounds of the formula I  
                 
 
     in which  
     R 1 , A 1 , A 2 , Z 1 , Z 2 , X, a, b, L 1 , L 2  and L 3  are as defined herein, and to liquid-crystalline media comprising at least one compound of the formula I and to electro-optical displays containing a liquid-crystalline medium of this type.

[0001] The present invention relates to liquid-crystalline compounds and to a liquid-crystalline medium, to the use thereof for electro-optical purposes, and to displays containing this medium.

[0002] Liquid-crystals are used principally as dielectrics in display devices, since the optical properties of such substances can be modified by an applied voltage. Electro-optical devices based on liquid crystals are extremely well known to the person skilled in the art and can be based on various effects. Examples of such devices are cells having dynamic scattering, DAP (deformation of aligned phases) cells, guest/host cells, TN cells having a twisted nematic structure, STN (supertwisted nematic) cells, SBE (super-birefringence effect) cells and OMI (optical mode interference) cells. The most common display devices are based on the Schadt-Helfrich effect and have a twisted nematic structure.

[0003] The liquid-crystal materials must have good chemical and thermal stability and good stability to electric fields and electromagnetic radiation. Furthermore, the liquid-crystal materials should have low viscosity and produce short addressing times, low threshold voltages and high contrast in the cells.

[0004] They should furthermore have a suitable mesophase, for example a nematic or cholesteric mesophase for the above-mentioned cells, at the usual operating temperatures, i.e. in the broadest possible range above and below room temperature. Since liquid crystals are generally used as mixtures of a plurality of components, it is important that the components are readily miscible with one another. Further properties, such as the electrical conductivity, the dielectric anisotropy and the optical anisotropy, have to satisfy various requirements depending on the cell type and area of application. For example, materials for cells having a twisted nematic structure should have positive dielectric anisotropy and low electrical conductivity.

[0005] For example, for matrix liquid-crystal displays with integrated non-linear elements for switching individual pixels (MLC displays), media having large positive dielectric anisotropy, broad nematic phases, relatively low birefringence, very high specific resistance, good UV and temperature stability and low vapor pressure are desired.

[0006] Matrix liquid-crystal displays of this type are known. Non-linear elements which can be used for individual switching of the individual pixels are, for example, active elements (i.e. transistors). The term “active matrix” is then used, where a distinction can be made between two types:

[0007] 1. MOS (metal oxide semiconductor) or other diodes on a silicon wafer as substrate.

[0008] 2. Thin-film transistors (TFTs) on a glass plate as substrate.

[0009] The use of single-crystal silicon as substrate material restricts the display size, since even modular assembly of various part-displays results in problems at the joins.

[0010] In the case of the more promising type 2, which is preferred, the electro-optical effect used is usually the TN effect. A distinction is made between two technologies: TFTs comprising compound semiconductors, such as, for example, CdSe, or TFTs based on polycrystalline or amorphous silicon. Intensive work is being carried out world-wide on the latter technology.

[0011] The TFT matrix is applied to the inside of one glass plate of the display, while the other glass plate carries the transparent counterelectrode on its inside. Compared with the size of the pixel electrode, the TFT is very small and has virtually no adverse effect on the image. This technology can also be extended to fully color-capable displays, in which a mosaic of red, green and blue filters is arranged in such a way that a filter element is opposite each switchable pixel.

[0012] The TFT displays usually operate as TN cells with crossed polarizers in transmission and are illuminated from the back.

[0013] The term MLC displays here covers any matrix display with integrated non-linear elements, i.e., besides the active matrix, also displays with passive elements, such as varistors or diodes (MIM=metal-insulator-metal).

[0014] MLC displays of this type are particularly suitable for TV applications (for example pocket TVs) or for high-information displays for computer applications (laptops) and in automobile or aircraft construction. Besides problems regarding the angle dependence of the contrast and the response times, difficulties also arise in MLC displays due to insufficiently high specific resistance of the liquid-crystal mixtures [TOGASHI, S., SEKIGUCHI, K., TANABE, H., YAMAMOTO, E., SORIMACHI, K., TAJIMA, E., WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, September 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, p. 141 ff, Paris; STROMER, M., Proc. Eurodisplay 84, September 1984: Design of Thin Film Transistors for Matrix Addressing of Television Liquid Crystal Displays, p. 145 ff, Paris]. With decreasing resistance, the contrast of an MLC display deteriorates, and the problem of after-image elimination may occur. Since the specific resistance of the liquid-crystal mixture generally drops over the life of an MLC display owing to interaction with the interior surfaces of the display, a high (initial) resistance is very important in order to obtain acceptable service lives. In particular in the case of low-volt mixtures, it was hitherto impossible to achieve very high specific resistance values. It is furthermore important that the specific resistance exhibits the smallest possible increase with increasing temperature and after heating and/or UV exposure. The low-temperature properties of the mixtures from the prior art are also particularly disadvantageous. It is demanded that no crystallisation and/or smectic phases occur, even at low temperatures, and the temperature dependence of the viscosity is as low as possible. The MLC displays from the prior art thus do not meet today's requirements.

[0015] There thus continues to be a great demand for MLC displays having very high specific resistance at the same time as a large working-temperature range, short response times even at low temperatures and low threshold voltage which do not have these disadvantages, or only do so to a reduced extent.

[0016] In TN (Schadt-Helfrich) cells, media are desired which facilitate the following advantages in the cells:

[0017] extended nematic phase range (in particular down to low temperatures)

[0018] the ability to switch at extremely low temperatures (outdoor use, automobile, avionics)

[0019] increased resistance to UV radiation (longer service life)

[0020] high Δn for faster response times

[0021] The media available from the prior art do not allow these advantages to be achieved while simultaneously retaining the other parameters.

[0022] In the case of supertwisted (STN) cells, media are desired which enable greater multiplexability and/or lower threshold voltages and/or broader nematic phase ranges (in particular at low temperatures). To this end, a further widening of the available parameter latitude (clearing point, smectic-nematic transition or melting point, viscosity, dielectric parameters, elastic parameters) is urgently desired.

[0023] The invention has an object of providing media, in particular for MLC, IPS, TN or STN displays of this type, which do not have the above-mentioned disadvantages or only do so to a reduced extent, and preferably simultaneously have very high specific resistances and low threshold voltages. This object requires liquid-crystalline compounds which have a high clearing point and low rotational viscosity.

[0024] Upon further study of the specification and appended claims, further objects and advantages of this invention will become apparent to those skilled in the art.

[0025] It has now been found that these objects and others can be achieved if the liquid-crystalline compounds according to the invention are used.

[0026] The invention thus relates to liquid-crystalline compounds of the formula I

[0027] in which

[0028] R is H, an alkenyl radical having from 2 to 15 carbon atoms which is unsubstituted, monosubstituted by CN or CF₃ or at least monosubstituted by halogen, where, in addition, one or more CH₂ groups in these radicals may be replaced by —O—, —S—, —CH═CH—, —C≡—C—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another,

[0029] A¹ and A² are each, independently of one another,

[0030] a) a 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH₂ groups may be replaced by —O— or —S—,

[0031] b) a 1,4-phenylene radical, in which one or two CH groups may be replaced by N,

[0032] c) a radical from the group consisting of piperidine-1,4-diyl, 1,4-bicyclo[2.2.2]octylene, phenanthrene-2,7-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl and fluorene-2,7-diyl,

[0033] where the radicals a), b) and c) may be monosubstituted or polysubstituted by halogen atoms,

[0034] X is F, Cl, CN, NCS, SF₅, or a halogenated or unsubstituted alkyl, alkoxy, alkenyloxy or alkenyl radical having up to 5 carbon atoms,

[0035] Z¹ and Z² are each, independently of one another, —CO—O—, —O—CO—, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—, —CH₂CH₂—, —(CH₂)₄—, —C₂F₄—, —CH₂CF₂—, —CF₂CH₂—, —CF═CF—, —CH═CH—, —C≡C— or a single bond, with the proviso that at least one of the bridges Z¹ and Z² is —CF₂O— or —OCF₂—,

[0036] a is 0, 1 or 2,

[0037] b is0, 1 or 2, and

[0038] L¹, L² and L³ are each, independently of one another, H, F or Cl.

[0039] The invention furthermore relates to the use of the compounds of the formula I in liquid-crystalline media.

[0040] The compounds of the formula I have a broad range of applications. Depending on the choice of substituents, these compounds can serve as base materials of which liquid-crystalline media are predominantly composed; however, it is also possible to add compounds of the formula I to liquid-crystalline base materials from other classes of compound in order, for example, to modify the dielectric and/or optical anisotropy of a dielectric of this type and/or in order to optimize its threshold voltage and/or its viscosity.

[0041] In the pure state, the compounds of the formula I are colorless and form liquid-crystalline mesophases in a temperature range which is favorably located for electro-optical use. In particular, the compounds according to the invention are distinguished by their broad nematic phase range. In liquid-crystalline mixtures, the substances according to the invention suppress the smectic phases and result in a clear improvement in the low-temperature storage stability. They are stable chemically, thermally and to light.

[0042] The invention relates in particular to the compounds of the formula I in which R is vinyl, CH₃CH═CH, CH₂═CHCH₂CH₂ or CH₃CH₂═CHCH₂CH₂.

[0043] Particular preference is given to compounds of the formula I in which a=b=1 or a=b=2. Z¹ or Z² is preferably a single bond, furthermore —CF₂O—, —OCF₂—, —C₂F₄—, —CH₂O—, —OCH₂— or —COO—.

[0044] The alkenyl radical R may be straight-chain or branched. It is preferably straight-chain and has from 2 to 10 carbon atoms. Accordingly, it is in particular vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, 4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, or dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.

[0045] If R is an alkenyl radical which is monosubstituted by CN or CF₃, this radical is preferably straight-chain. The substitution by CN or CF₃ is, in any desired position.

[0046] If R is an alkenyl radical which is at least monosubstituted by halogen, this radical is preferably straight-chain, and halogen is preferably F or Cl. In the case of polysubstitution, halogen is preferably F. The resultant radicals also include perfluorinated radicals. In the case of monosubstitution, the fluorine or chlorine substituent may be in any desired position, but is preferably in the ω-position.

[0047] Compounds of the formula I containing branched wing groups R may occasionally be of importance owing to better solubility in the conventional liquid-crystalline base materials, but in particular as chiral dopants if they are optically active. Smectic compounds of this type are suitable as components of ferroelectric materials.

[0048] Compounds of the formula I having S_(A) phases are suitable for thermally addressed displays.

[0049] For reasons of simplicity, Cyc below denotes a 1,4-cyclohexylene radical, Che denotes a 1,4-cyclohexenylene radical, Dio denotes a 1,3-dioxane-2,5-diyl radical, Dit denotes a 1,3-dithiane-2,5-diyl radical, Phe denotes a 1,4-phenylene radical, Pyd denotes a pyridine-2,5-diyl radical, Pyr denotes a pyrimidine-2,5-diyl radical, Bi denotes a bicyclo[2.2.2]octylene radical, PheF denotes a 2- or 3-fluoro-1,4-phenylene radical, PheFF denotes a 2,3-difluoro- or 2,6-difluoro-1,4-phenylene radical, Nap denotes a substituted or unsubstituted naphthalene radical, Dec denotes a decahydronaphthalene radical, and Phen denotes a substituted or unsubstituted phenanthrene radical.

[0050] For reasons of simplicity, A³—X below denotes

[0051] The compounds of the formula I accordingly include the preferred bicyclic compounds of the sub-formulae Ia to Ij:

[0052] (Z²=—CF₂O— or —OCF₂—): R-Cyc-Z²-A³-X Ia R-Phe-Z²-A³-X Ib R-Pyr-Z²-A³-X Ic R-Dio-Z²-A³-X Id R-Bi-Z²-A³-X Ie R-PheF-Z²-A³-X If R-PheFF-Z²-A³-X Ig R-Nap-Z²-A³-X Ih R-Dec-Z²-A³-X Ii R-Phen-Z²-A³-X Ij

[0053] The compounds of the formula I accordingly include the preferred tricyclic compounds of the sub-formulae Ik to Iv:

[0054] (Z¹ or Z²: —CF₂O— or —OCF₂—): R-Cyc-Z¹-Cyc-Z²-A³-X Ik R-Cyc-Z¹-Phe-Z²-A³-X Il R-Cyc-Z¹-PheF-Z²-A³-X Im R-Cyc-Z¹-PheFF-Z²-A³-X In R-Phe-Z¹-Phe-Z²-A³-X Io R-Cyc-Z¹-Dio-Z²-A³-X Ip R-Dio-Z¹-Cyc-Z²-A³-X Iq R-Dec-Z¹-Cyc-Z²-A³-X Ir R-Phe-Z¹-PheF-Z²-A³-X Is R-Phe-Z¹-PheFF-Z²-A³-X It R-Pyr-Z¹-Phe-Z²-A³-X Iu R-Phe-Z¹-Phen-Z²-A³-X Iv

[0055] Of these, particular preference is given to the compounds of the sub-formulae Ia, Ib, Id, Ik, and Il.

[0056] A¹ and A² are preferably Phe, PheF, PheFF, Cyc or Che, furthermore Pyr or Dio, Dec or Nap. The compounds of the formula I preferably contain not more than one of the radicals Bi, Pyd, Pyr, Dio, Dit, Nap or Dec.

[0057] Preference is also given to all compounds of the formula I and of all sub-formulae in which A¹ and A² are a monosubstituted or disubstituted 1,4-phenylene. These are, in particular, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene and 2,6-difluoro-1,4-phenylene.

[0058] Preferred subgeneric groups of compounds of the formula I are those of the sub-formulae I1 to I105:

[0059] wherein (F) means fluorine or hydrogen.

[0060] The compounds of the formula I are prepared by methods known per se, as described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and suitable for the said reactions. Use can also be made here of variants which are known per se, but are not mentioned here in greater detail.

[0061] The compounds according to the invention can be prepared, for example, as follows:

[0062] The invention also relates to electro-optical displays (in particular STN or MLC displays having two plane-parallel outer plates, which, together with a frame, form a cell, integrated non-linear elements for switching individual pixels on the outer plates, and a nematic liquid-crystal mixture of positive dielectric anisotropy and high specific resistance which is located in the cell) which contain media of this type, and to the use of these media for electro-optical purposes.

[0063] The liquid-crystal mixtures according to the invention enable a significant widening of the available parameter latitude.

[0064] The achievable combinations of clearing point, viscosity at low temperature, thermal and UV stability and dielectric anisotropy are far superior to previous materials from the prior art.

[0065] The requirement for a high clearing point, a nematic phase at low temperature and a high Δ∈ has hitherto only been achieved to an inadequate extent. Although liquid-crystal mixtures such as, for example, MLC-6476 and MLC-6625 (Merck KGaA, Darmstadt, Germany) have comparable clearing points and low-temperature stabilities, they have, however, relatively low Δn values and also higher threshold voltages of about ≧1.7 V.

[0066] Other mixture systems have comparable viscosities and Δ∈ values, but only have clearing points in the region of 60° C.

[0067] The liquid-crystal mixtures according to the invention, while retaining the nematic phase down to −20° C. and preferably down to −30° C., particularly preferably down to −40° C., enable clearing points above 80° C., preferably above 90° C., particularly preferably above 100° C., simultaneously dielectric anisotropy values Δ∈ of ≧4, preferably ≧6, and a high value for the specific resistance to be achieved, enabling excellent STN and MLC displays to be obtained. In particular, the mixtures are characterised by low operating voltages. The TN thresholds are below 1.5 V, preferably below 1.3 V.

[0068] It goes without saying that, through a suitable choice of the components of the mixtures according to the invention, it is also possible for higher clearing points (for example above 110°) to be achieved at a higher threshold voltage or lower clearing points to be achieved at lower threshold voltages with retention of the other advantageous properties. At viscosities correspondingly increased only slightly, it is likewise possible to obtain mixtures having greater Δ∈ and thus lower thresholds. The MLC displays according to the invention preferably operate at the first Gooch and Tarry transmission minimum [C. H. Gooch and H. A. Tarry, Electron. Lett. 10, 2-4, 1974; C. H. Gooch and H. A. Tarry, Appl. Phys., Vol. 8,1575-1584, 1975] are used, where, besides particularly favorable electro-optical properties, such as, for example, high steepness of the characteristic line and low angle dependence of the contrast (German Patent 30 22 818), a lower dielectric anisotropy is sufficient at the same threshold voltage as in an analogous display at the second minimum. This enables significantly higher specific resistances to be achieved using the mixtures according to the invention at the first minimum than in the case of mixtures comprising cyano compounds. Through a suitable choice of the individual components and their proportions by weight, the person skilled in the art is able to set the birefringence necessary for a pre-specified layer thickness of the MLC display using simple routine methods.

[0069] The flow viscosity ν₂₀ at 20° C. is preferably <60 mm²·s⁻¹, particularly preferably <50 mm²·s⁻¹. The nematic phase range is preferably at least 90°, in particular at least 100°. This range preferably extends at least from −30° to +80°.

[0070] Measurements of the capacity holding ratio (HR) [S. Matsumoto et al., Liquid Crystals 5, 1320 (1989); K. Niwa et al., Proc. SID Conference, San Francisco, June 1984, p. 304 (1984); G. Weber et al., Liquid Crystals 5, 1381 (1989)] have shown that mixtures according to the invention comprising compounds of the formula I exhibit a significantly smaller decrease in the HR with increasing temperature than, for example, analogous mixtures comprising cyanophenylcyclohexanes of the formula

[0071] or esters of the formula

[0072] instead of the compounds of the formula I.

[0073] The UV stability of the mixtures according to the invention is also considerably better, i.e. they exhibit a significantly smaller decrease in the HR on exposure to UV.

[0074] The media according to the invention are preferably based on a plurality of (preferably two, three or more) compounds of the formula I, i.e. the proportion of these compounds is 5-95%, preferably 10-60% and particularly preferably in the range 15-40%.

[0075] The individual compounds of the formulae I to IX and their sub-formulae which can be used in the media according to the invention are either known or they can be prepared analogously to the known compounds. Preferred embodiments are indicated below:

[0076] The medium preferably comprises one, two or three homologous compounds of the formula I, where each homologue is present in the mixture in a maximum proportion of 10%.

[0077] Medium additionally comprises one or more compounds selected from the group consisting of the general formulae II to IX:

[0078] in which the individual radicals have the following meanings:

[0079] R⁰ is n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl, each having up to 9 carbon atoms,

[0080] X⁰ is F, Cl, halogenated alkyl, halogenated alkenyl, halogenated alkenyloxy or halogenated alkoxy having up to 7 carbon atoms,

[0081] Z⁰ is —CH═CH—, —C₂H₄—, —(CH₂)₄—, —C₂F₄—, —CF═CF—, —CF₂O—, —OCF₂— or —COO—,

[0082] Y¹, Y²,

[0083] Y³ and Y⁴ are each, independently of one another, H or F, and

[0084] r is 0 or 1.

[0085] The compound of the formula IV is preferably

[0086] The medium additionally comprises one or more compounds of the formulae

[0087] in which R⁰ and Y² are as defined above.

[0088] The medium preferably comprises one, two or three, furthermore four, homologues of the compounds selected from the group consisting of H1 to H18 (n=1-7):

[0089] The medium additionally comprises one or more compounds selected from the group consisting of the general formulae X to XV:

[0090] in which R⁰, X⁰, Y¹, Y², Y³ and Y⁴ are each, independently of one another, as defined in claim 7. X⁰ is preferably F, Cl, CF₃, OCF₃ or OCHF₂. R⁰ is preferably alkyl, oxaalkyl, fluoroalkyl, alkenyl or alkenyloxy.

[0091] The proportion of compounds of the formulae I to IX together in the mixture as a whole is at least 50% by weight.

[0092] The proportion of compounds of the formula I in the mixture as a whole is from 5 to 50% by weight.

[0093] The proportion of compounds of the formulae II to IX in the mixture as a whole is from 30 to 70% by weight.

[0094] The medium comprises compounds of the formulae II, III, IV, V, VI, VII, VII and/or IX.

[0095] R⁰ is straight-chain alkyl or alkenyl having from 2 to 7 carbon atoms.

[0096] The medium essentially consists of compounds of the formulae I to XV.

[0097] The medium comprises further compounds, preferably selected from the following group consisting of the general formulae XVI to XX:

[0098] in which R⁰ and X⁰ are as defined above, and the 1,4-phenylene rings may be substituted by CN, chlorine or fluorine. The 1,4-phenylene rings are preferably monosubstituted or polysubstituted by fluorine atoms.

[0099] The medium comprises further compounds, preferably selected from the following group consisting of the formulae RI to RXI

[0100] in which

[0101] R⁰ is n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl, each having up to 9 carbon atoms,

[0102] d is 0, 1 or 2,

[0103] Y¹ is H or F,

[0104] alkyl and

[0105] alkyl* are each, independently of one another, a straight-chain or branched alkyl radical having 1-9 carbon atoms,

[0106] alkenyl and

[0107] alkenyl* are each, independently of one another, a straight-chain or branched alkenyl radical having up to 9 carbon atoms.

[0108] The medium preferably comprises one or more compounds of the formulae

[0109] in which n and m are each an integer from 1-9.

[0110] The I:(II+III+IV+V+VI+VII+VII+IX) weight ratio is preferably from 1:10 to 10:1.

[0111] The medium essentially consists of compounds selected from the group consisting of the general formulae I to XV.

[0112] It has been found that even a relatively small proportion of compounds of the formula I mixed with conventional liquid-crystal materials, but in particular with one or more compounds of the formulae II, III, IV, V, VI, VII, VIII and/or IX, results in a significant lowering of the threshold voltage and in low birefringence values, with broad nematic phases with low smectic-nematic transition temperatures being observed at the same time, improving the shelf life. The compounds of the formulae I to IX are colorless, stable and readily miscible with one another and with other liquid-crystalline materials.

[0113] The term “alkyl” or “alkyl*” covers straight-chain and branched alkyl groups having 1-9 carbon atoms, in particular the straight-chain groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. Groups having 2-5 carbon atoms are generally preferred.

[0114] The term “alkenyl” or “alkenyl*” covers straight-chain and branched alkenyl groups having up to 9 carbon atoms, in particular the straight-chain groups. Preferred alkenyl groups are C₂-C₇-1E-alkenyl, C₄-C₇-3E-alkenyl, C₅-C₇-4-alkenyl, C₆-C₇-5-alkenyl and C₇-6-alkenyl, in particular C₂-C₇-1E-alkenyl, C₄-C₇-3E-alkenyl and C₅-C₇-4-alkenyl. Examples of particularly preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred.

[0115] The term “fluoroalkyl” preferably covers straight-chain groups having a terminal fluorine, i.e. fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. However, other positions of the fluorine are not excluded.

[0116] The term “oxaalkyl” preferably covers straight-chain radicals of the formula C_(n)H_(2n+1)—O—(CH₂)_(m), in which n and m are each, independently of one another, from 1 to 6. n is preferably=1 and m is preferably from 1 to 6.

[0117] Through a suitable choice of the meanings of R⁰ and X⁰, the addressing times, the threshold voltage, the steepness of the transmission characteristic lines, etc., can be modified in the desired manner. For example, 1E-alkenyl radicals, 3E-alkenyl radicals, 2E-alkenyloxy radicals and the like generally result in shorter addressing times, improved nematic tendencies and a higher ratio of the elastic constants k₃₃ (bend) and k₁₁ (splay) compared with alkyl or alkoxy radicals. 4-alkenyl radicals, 3-alkenyl radicals and the like generally give lower threshold voltages and smaller values of k₃₃/k₁₁ compared with alkyl and alkoxy radicals.

[0118] A —CH₂CH₂— group in Z¹ and/or Z² generally results in higher values of k₃₃/k₁₁ compared with a single covalent bond. Higher values of k₃₃/k₁₁ facilitate, for example, flatter transmission characteristic lines in TN cells with a 90° twist (in order to achieve grey shades) and steeper transmission characteristic lines in STN, SBE and OMI cells (greater multiplexability), and vice versa.

[0119] The optimum mixing ratio of the compounds of the formulae I and II+III+IV+V+VI+VII+VIII+IX depends substantially on the desired properties, on the choice of the components of the formulae I, II, III, IV, V, VI, VII, VIII and/or IX, and the choice of any other components that may be present. Suitable mixing ratios within the range given above can easily be determined from case to case.

[0120] The total amount of compounds of the formulae I to XV in the mixtures according to the invention is not crucial. The mixtures can therefore comprise one or more further components for the purposes of optimising various properties. However, the observed effect on the addressing times and the threshold voltage is generally greater, the higher the total concentration of compounds of the formulae I to XV.

[0121] In a particularly preferred embodiment, the media according to the invention comprise compounds of the formulae II to IX (preferably II and/or III) in which X⁰ is OCF₃, OCHF₂, F, OCH═CF₂, OCF═CF₂, OCF₂CHFCF₃ or OCF₂—CF₂H. A favorable synergistic effect with the compounds of the formula I results in particularly advantageous properties.

[0122] The construction of the MLC display according to the invention from polarizers, electrode base plates and surface-treated electrodes corresponds to the conventional construction for displays of this type. The term “conventional construction” is broadly drawn here and also covers all derivatives and modifications of the MLC display, in particular including matrix display elements based on poly-Si TFT or MIM.

[0123] A significant difference between the displays according to the invention and the conventional displays based on the twisted nematic cell consists, however, in the choice of the liquid-crystal parameters of the liquid-crystal layer.

[0124] The liquid-crystal mixtures which can be used in accordance with the invention are prepared in a manner conventional per se. In general, the desired amount of the components used in the lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. It is also possible to mix solutions of the components in an organic solvent, for example in acetone, chloroform or methanol, and to remove the solvent again, for example by distillation, after thorough mixing.

[0125] The dielectrics may also comprise further additives known to the person skilled in the art and described in the literature, such as, for example, stabilisers and antioxidants. For example, 0-15% of pleochroic dyes or chiral dopants can be added.

[0126] C denotes a crystalline phase, S a smectic phase, S_(C) a smectic C phase, S_(B) a smectic B phase, N a nematic phase and I the isotropic phase.

[0127] V₁₀ denotes the voltage for 10% transmission (viewing angle perpendicular to the plate surface). t_(on) denotes the switch-on time and t_(off) the switch-off time at an operating voltage corresponding to 2 times the value of V₁₀. Δn denotes the optical anisotropy and n₀ the refractive index. Δ∈ denotes the dielectric anisotropy (Δ∈=∈_(∥)−∈_(⊥), where ∈_(∥) denotes the dielectric constant parallel to the longitudinal molecular axes and ∈_(⊥) denotes the dielectric constant perpendicular thereto). The electro-optical data were measured in a TN cell at the 1 st minimum (i.e. at a d·Δn value of 0.5) at 20° C., unless expressly stated otherwise. The optical data were measured at 20° C., unless expressly stated otherwise.

[0128] The entire disclosures of all applications, patents and publications, cited herein and of corresponding German application No. 10148356.2, filed Sep. 29, 2001 are incorporated by reference herein.

[0129] Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

[0130] In the foregoing and in the following examples, all temperatures are set forth uncorrected in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.

EXAMPLES

[0131] In the present application and in the examples below, the structures of the liquid-crystal compounds are indicated by means of acronyms, the transformation into chemical formulae taking place in accordance with Tables A and B below. All radicals C_(n)H_(2n+1) and C_(m)H_(2m+1) are straight-chain alkyl radicals having n and m carbon atoms respectively; n and m are in each case, independently of one another, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15. The coding in Table B is self-evident. In Table A, only the acronym for the parent structure is indicated. In individual cases, the acronym for the parent structure is followed, separated by a dash, by a code for the substituents R¹, R², L¹ and L²: Code for R¹, R², L¹, L² R¹ R² L¹ L² nm C_(n)H_(2n+1) C_(m)H_(2m+1) H H nOm C_(n)H_(2n+1) OC_(m)H_(2m+1) H H nO.m OC_(n)H_(2n+1) C_(m)H_(2m+1) H H n C_(n)H_(2n+1) CN H H nN.F C_(n)H_(2n+1) CN H F nF C_(n)H_(2n+1) F H H nOF OC_(n)H_(2n+1) F H H nCl C_(n)H_(2n+1) Cl H H nF.F C_(n)H_(2n+1) F H F nF.F.F C_(n)H_(2n+1) F F F nCF₃ C_(n)H_(2n+1) CF₃ H H nOCF₃ C_(n)H_(2n+1) OCF₃ H H nOCF₂ C_(n)H_(2n+1) OCHF₂ H H nS C_(n)H_(2n+1) NCS H H rVsN C_(r)H_(2r+1)—CH═CH—C_(s)H_(2s)— CN H H rEsN C_(r)H_(2r+1)—O—C₂H_(2s)— CN H H nAm C_(n)H_(2n+1) COOC_(m)H_(2m+1) H H nOCCF₂.F.F C_(n)H_(2n+1) OCH₂CF₂H F F

[0132] Preferred mixture components are shown in Tables A and B. TABLE A

PYP

PYRP

BCH

CBC

CCH

CCP

CPTP

CEPTP

ECCP

CECP

EPCH

PCH

PTP

BECH

EBCH

CPC

B

FET-nF

CGG

CGU

CUP

CCQU

PGU

[0133] TABLE B

CBC-nmF

PCH-nOm FET-nCl

CP-nOCF₃

CCH-nOm BCH-n.FX

Inm

CBC-nmF

ECCP-nm CCH-n1EM

T-nFm CGU-n-F

CCP-nOCF₃.F CGG-n-F

CCP-nOCF₂.F(.F) CCP-nF.F.F

CGU-n-OXF

CUZU-n-F CGU-n-O1DT

CGU-n-O1DT CC-n-V1

CC-n-V CCP-nOCF₃

BCH-nF.F.F

CWCZU-n-F

CWCZG-n-F

CCOC-n-m

CGZU-n-F CUZP-n-F

CGU-1V-F CCG-V-F

CGZP-n-F UZP-n-N

CGZP-n-OT

CUZP-n-OT

CCQU-n-F Dec-U-n-F

Nap-U-n-F

CQGZP-n-F

CCQP-n-S

CPUQU-n-F

CCEEU-n-F CEECU-n-F

CCQU-V-F CCQU-1V-F

PUQU-V2-F

[0134] TABLE C Table C shows possible dopants which are generally added to the mixtures according to the invention.

C 15

CB 15

CM 21

R/S-811

CM 44

CM 45

CM 47

CN

R/S-4011

R/S-2011

[0135] TABLE D Stabilisers which can be added, for example, to the mixtures according to the invention are mentioned below.

[0136] The following examples are intended to explain the invention without restricting it. Above and below, percentages are per cent by weight. All temperatures are given in degrees Celsius. m.p. denotes melting point, cl.p. denotes clearing point. Furthermore, C=crystalline state, N=nematic phase, S=smectic phase and I=isotropic phase. The data between these symbols represent the transition temperatures. Δn denotes optical anisotropy (589 nm, 20° C.), the flow viscosity ν₂₀ ((mm²/sec) was determined at 20° C. The rotational viscosity γ₁ [mPa·s] was likewise determined at 20° C.

[0137] “Conventional work-up” means that water is added if necessary, the mixture is extracted with dichoromethane, diethyl ether, methyl tert-butyl ether or toluene, the phases are separated, the organic phase is dried and evaporated, and the product is purified by distillation under reduced pressure or crystallisation and/or chromatography. The following abbreviations are used: n-BuLi 1.6 molar solution of n-butyllithium in n-hexane DMAP 4-(dimethylamino)pyridine THF tetrahydrofuran DCC N,N′-dicyclohexylcarbodiimide LDA lithium dimethylamide

Example 1

[0138]

[0139] 0.780 mol of B in 2.5 l of abs. THF are initially introduced and cooled to −70° C. At −70° C., 0.780 mol of n-BuLi (15% solution in n-hexane) is added dropwise, and the mixture is stirred at −70° C. for 0.5 hour and warmed slowly to −15° C. After 0.78 mol of A has been added at −70° C., the mixture is stirred overnight at room temperature. Methyl tert-butyl ether and NaHCO₃ solution are added to the mixture, which is subjected to conventional work-up. The crude product is recrystallised from n-heptane.

[0140] 0.1 mol of C is dissolved in 300 ml of dichloromethane, and 0.1 mol of trifluoromethanesulfonic acid is added with ice cooling. The reaction mixture is stirred at 5° C., allowed to warm to room temperature and stirred for a further 2 hours. A mixture of 0.15 mol of 3,4,5-trifluorophenol and 0.18 mol of triethylamine in 30 ml of dichloromethane is added dropwise to the reaction mixture at −70° C., and the mixture is subsequently stirred at −70° C. for 1 hour. After 0.5 mol of triethylamine trishydrofluoride has been added, a mixture of 1,3-dibromo-5,5-dimethylhydantoin in 170 ml of dichloromethane is added in portions. The mixture is stirred at −70° C. for a further 1 hour, and 300 ml of a 1 molar NaOH solution are added at −20° C. The aqueous phase is separated off and extracted with dichloromethane. The combined organic phases are subjected to conventional work-up.

[0141] 200 ml of formic acid are added to 0.083 mol of D dissolved in 250 ml of abs. toluene, and the mixture is stirred overnight at room temperature. The formic acid is separated off and extracted with toluene. The combined organic phases are subjected to conventional work-up. The residue is recrystallised from n-heptane.

[0142] 0.013 mol of E and 0.019 mol of methoxymethyltriphenylphosphonium chloride in 300 ml of abs. THF are introduced into an inert apparatus and cooled at −5° C. After 0.019 mol of potassium tert-butoxide in 50 ml of abs. THF has been added, the mixture is stirred at 0° C. for 1 hour and at room temperature overnight. After H₂O and a few drops of dilute HCl have been added, the organic phase is separated off and subjected to conventional work-up.

[0143] 200 ml of formic acid are added to 0.083 mol of F dissolved in 250 ml of abs. toluene, and the mixture is stirred overnight at room temperature. The formic acid is separated off and extracted with toluene. The combined organic phases are subjected to conventional work-up. The residue is recrystallised from n-heptane.

[0144] 2.82 mmol of G and 3.36 mmol of methyltriphenylphosphonium bromide are dissolved in 40 ml of abs. THF and cooled to 2° C. 3.36 mmol of potassium tert-butoxide in 20 ml of abs. THF are added dropwise to this solution and dissolved overnight at room temperature. The triphenylphosphine oxide is filtered off with suction, and the filtrate is evaporated to dryness. The crude product, dissolved in n-heptane, is filtered through a silica frit, and the filtrate is re-evaporated. The residue is recrystallised from n-pentane at −20° C. C, 29; N, 88.4; I; Δn=0.0761; Δ∈=8.3.

[0145] The following compounds of the formula

[0146] are prepared analogously: X L¹ L² F H H F F H OCF₃ H H OCF₃ F H OCF₃ F F OCH₂CF₃ H H OCH₂CF₃ F H OCH₂CF₃ F F Cl H H Cl F H Cl F F CN H H CN F H CN F F SF₅ H H SF₅ F H SF₅ F F NCS H H NCS F H NCS F F OCHF₂ H H OCHF₂ F H OOHF₂ F F CF₃ H H CF₃ F H CF₃ F F OCF₂CHFCF₃ H H OCF₂CHFCF₃ F H OCF₂CHFCF₃ F F OC₃F₇ H H OC₃F₇ F H OC₃F₇ F F C₃F₇ H H C₃F₇ F H C₃F₇ F F

Mixture Examples Example M1

[0147] BCH-3F.F 10.80% Clearing point [° C.]: 90.3 BCH-5F.F 9.00% Δn [589 nm, 20° C.]: 0.0945 ECCP-30CF₃ 4.50% Δε [1 kHz, 20° C.]: 5.6 ECCP-50CF₃ 4.50% CBC-33F 1.80% CBC-53F 1.80% CBC-55F 1.80% PCH-6F 7.20% PCH-7F 5.40% CCP-20CF₃ 7.20% CCP-30CF₃ 10.80% CCP-40CF₃ 6.30% CCP-50CF₃ 9.90% PCH-5F 9.00% CCQU-V-F 10.00%

Example M2

[0148] CCP-2F.F.F 12.00% Clearing point [° C.]: 76 CCP-3F.F.F 10.00% Δn [589 nm, 20° C.]: 0.0916 CCP-5F.F.F 1.00% V_(10,0,20): 1.23 CCP-20CF₃ 8.00% γ₁: 152 CCP-30CF₃ 8.00% CCP-40CF₃ 7.00% CCP-50CF₃ 7.00% CGU-2-F 12.00% CGU-3-F 10.00% CGU-5-F 10.00% CCQU-V-F 15.00%

Example M3

[0149] CCP-2F.F.F 12.00% Clearing point [° C.]: 75.7 CCP-3F.F.F 10.00% Δn [589 nm, 20° C.]: 0.0928 CCP-5F.F.F 6.00% V_(10,0,20): 1.18 CCP-20CF₂.F.F 1.00% γ₁: 146 CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% CCP-40CF₃ 7.00% CGU-2-F 12.00% CGU-3-F 10.00% CWCQU-2-F 5.50% PGU-2-F 5.50% CCQU-V-F 15.00%

Example M4

[0150] CCP-2F.F.F 12.00% Clearing point [° C.]: 75 CCP-3F.F.F 10.00% Δn [589 nm, 20° C.]: 0.0932 CCP-20CF₃ 8.00% V_(10,0,20): 1.17 CCP-30CF₃ 8.00% γ₁: 139 CCP-40CF₃ 7.00% CCP-50CF₃ 4.00% CGU-2-F 12.00% CGU-3-F 4.00% CCQU-2-F 12.00% PGU-2-F 8.00% CCQU-V-F 15.00%

Example M5

[0151] CCP-2F.F.F 12.00% Clearing point [° C.]: 76 CCP-3F.F.F 2.50% Δn [589 nm, 20° C.]: 0.0930 CCP-20CF₃ 8.00% V_(10,20): 1.20 CCP-30CF₃ 8.00% γ₁: 137 CCP-40CF₃ 7.00% CCP-50CF₃ 3.00% CGU-2-F 12.00% CGU-3-F 10.00% CCP-2F.F 9.00% CCP-3F.F 6.00% PGU-2-F 6.50% CCGU-3-F 1.00% CCQU-V-F 15.00%

Example M6

[0152] BCH-3F.F 10.80% Clearing point [° C.]: 81.7 BCH-5F.F 9.00% Δn [589 nm, 20° C.]: 0.0996 ECCP-30CF₃ 4.50% Δε [1 kHz, 20° C.]: 6.5 ECCP-50CF₃ 4.50% d*Δn [nm]: 0.5 CBC-33F 1.80% Twist: 90 CBC-53F 1.80% CBC-55F 1.80% PCH-6F 7.20% PCH-7F 5.40% CCP-20CF₃ 7.20% CCP-30CF₃ 10.80% CCP-40CF₃ 6.30% CCP-50CF₃ 9.90% PCH-5F 9.00% PUQU-V2-F 10.00%

[0153] The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

[0154] From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. 

Patent claims
 1. A liquid-crystalline compound of the formula I

in which R is H, an alkenyl radical having from 2 to 15 carbon atoms which is unsubstituted, monosubstituted by CN or CF₃ or mono- to perhalo- by halogen, where, one or more CH₂ groups in these radicals are optionally replaced by —O—, —S—, —CH═CH—, —C≡C—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another, A¹ and A² are each, independently of one another, a) a 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH₂ groups are optionally replaced by —O— or —S—, b) a 1,4-phenylene radical, in which one or two CH groups are optionally replaced by N, c) a radical selected from the group consisting of piperidine-1,4-diyl, 1,4-bicyclo[2.2.2]octylene, phenanthrene-2,7-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetra-hydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl and fluorene-2,7-diyl, where the radicals a), b) and c) are optionally mono- to perhalo- substituted by halogen atoms, X is F, Cl, CN, NCS, SF₅, or a halogenated or unsubstituted alkyl, alkoxy, alkenyloxy or alkenyl radical having 1 to 5 carbon atoms, Z¹ and Z² are each, independently of one another, —CO—O—, —O—CO—, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—, —CH₂CH₂—, —(CH₂)₄—, —C₂F₄—, —CH₂CF₂—, —CF₂CH₂—, —CF═CF—, —CH═CH—, —C≡C— or a single bond, with the proviso that at least one of the bridges Z¹ and Z² is —CF₂O— or —OCF₂—, a is 0, 1 or 2, b is 0, 1 or 2, and L¹, L² and L³ are each, independently of one another, H, F or Cl.
 2. A liquid-crystalline compound according to claim 1, wherein R is vinyl, CH₃CH═CH, CH₂═CHCH₂CH₂ or CH₃CH═CHCH₂CH₂.
 3. A liquid-crystalline compound according to claim 1, wherein a+b=1 or a+b=2.
 4. A liquid-crystalline compound according to claim 1, wherein L¹ is fluorine and L² is fluorine or hydrogen.
 5. A liquid-crystalline compound according to claim 4, wherein L² and L³ are fluorine.
 6. A liquid-crystalline compound according to claim 1, which is of one of the formulae I1 to I105:

in which R and X are as defined in claim 1 and (F) means fluorine or hydrogen.
 7. A liquid-crystalline medium comprising at least two mesogenic compounds, wherein at least one mesogenic compound is a compound of the formula I according to claim
 1. 8. An electro-optical liquid-crystal display which comprises a liquid-crystalline medium according to claim
 7. 9. A compound of the formula I of claim 1, wherein A¹ and A² are independently selected from Phe, PheF, PheFF, Cyc, Che, Pyr, Dio, Dec or Nap, provided that the compound does not contain more than one of Pyr, Dio, Dec, or Nap, where Cyc denotes a 1,4-cyclohexylene radical, Che denotes a 1,4-cyclohexenylene radical, Dio denotes a 1,3-dioxane-2,5-diyl radical, Phe denotes a 1,4-phenylene radical, Pyr denotes a pyrimidine-2,5-diyl radical, PheF denotes a 2- or 3-fluoro-1,4-phenylene radical, PheFF denotes a 2,3-difluoro- or 2,6-difluoro-1,4-phenylene radical, Nap denotes a substituted or unsubstituted naphthalene radical, and Dec denotes a decahydronaphthalene radical.
 10. A compound of the formula I of claim 1, wherein A¹ and A² are independently selected from monofluoro-substituted or difluoro-substituted 1,4-phenylene.
 11. A liquid-crystalline medium of claim 7, wherein the medium has a nematic phase down to −20° C., a clearing point above 80° C., a dielectric anisotropy, Δ∈, of ≧4.
 12. A liquid-crystalline medium of claim 11, wherein the medium has a TN threshold below 1.5 V.
 13. A liquid-crystalline medium of claim 7, wherein the medium contains 5-95% by weight of compounds of the formula I.
 14. A liquid-crystalline medium of claim 7, wherein the medium contains 10-60% by weight of compounds of the formula I. 